Dong-Sun Lee / cat - lab / SWU Copyright

2012 -Fall version

Chapter

21

Potentiometry

Electroanalytical techniques
1) 2) Ionics ---- Conductance lectro!ics

a) Static (I = 0) --- Potentiometry b) Dynamic (I 0) Controlled current --- Coulometric titration Controlled potential Stirred solution Controlled potential Hydrodynamic oltammetry !mperometry --- !mperometic titration "uiescent solution Potential scan --- Cyclic oltammetry# Polarography Small amplitude pulse techni$ue Di%%erential pulse oltammetry S$uare &a e oltammetry Potential step --- Chronoamperometry# Chronocoulometry Pulse oltammetry# Chronoabsorptometry

Classification of electrochemical methods

1" P#$ %$I#& $'( 'easure electrical potential de eloped by an electrode in an electrolyte solution at (ero current %lo&) *se +,-+S. ,"*!.I/+ relating potential to concentration o% some ion in solution) )#L$*&& $'( Determine concentration o% ion in dilute solutions %rom current %lo& as a %unction o% oltage &hen P/0!-I1!.I/+ o% ion occurs around the electrode) P/0!-I1!.I/+ = depletion o% concentration caused by electrolysis) I% using a dropping mercury electrode# method is termed P/0!-/2-!PH3) ,#UL#& $'( ,lectrolysis o% a solution and use o% 4araday5s la&6 relating $uantity o% electrical charge to amount o% chemical change) 76 essentially states that it ta8es 9):; < =0> Coulombs o% electrical charge to cause electrolysis o% = mole o% a uni alent electrolyte species)? ,#%DU,$I& $'( 'easure conductance o% a solution# using INERT ELECTRODES, ALTERNATING CURRENT, AND AN ELECTRICAL NULL CIRCUIT - thereby ensure no net current %lo& and no electrolysis) .he concentration o% ions in the solution is estimated %rom the conductance)
&et.o!s 1 an! -# %# L ,$'#L(SIS o% solution) Sample reco erable# unaltered by analysis) &et.o!s 2 an! + must cause L ,$'#L(SIS #F $/ S*&PL "

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Potentiometry
!n electroanalytical techni$ue based on the measurement o% the electromoti e %orce o% an electrochemical cell comprised o% a measuring and a re%erence electrode) .he simplest e<ample o% a measuring electrode is a metal electrode &hose potential depends on the concentration o% the cation o% the electrode metal)

Indicator electrode

,lectrochemical measuring system)

0eneral Princi1les
-e%erence electrode E salt bridge E analyte solution E indicator electrode ,re% ,B ,ind

,cell = ,ind F ,re% G ,B

-e%erence cell @ a half cell having a known electrode otential Indicator electrode@ ha! a otential that varie! in a known wa" with variation! in the concentration of an anal"te

! cell %or potentiometric determinations)

'e2erence electro!e
# $aintain! a fi%ed otential # a half cell having a known electrode otential

=) Saturate! calomel electro!e (S"," ")

Hg(l) E HgDClD (satHd)# ICl (satHd) E E

electrode reaction in calomel hal-cell HgDClD (s) G De = DHg(l) G DClF Eo = G 0)D:JK

E = Eo F (0)0;9=:AD) log7ClF?D = 0)D>> K

.emperature dependent
! calomel electrode saturated &ith ICl is called a saturated calomel electrode# abbre iated S"," " !d antage @ using saturated ICl is that 7Cl-? does not change i% some li$uid e aporates)

.he crystal structure o% calomel(HgDClD)# &hich has limited solubility in &ater (Isp = =)J L=0F=J))

HgDClD = HgDDG G DClF Isp = =)J L=0F=J

Saturated ICl = >): ' ICl

4ig) D=-D) Diagram o% a typical commercial saturated calomel electrode)

4ig) D=-C) ! saturated calomel electrode made %rom materials readily a ailable in any laboratory)

D) Silver-silver c.lori!e electro!e

!g(s) E !gCl (satHd)# ICl (%') E E

!gCl(s) G e = !g(s) G ClF Eo = G0)D>>K

E = Eo F (0)0;9=:A=) log 7ClF? E (saturated ICl) = G 0)=99K (D;oC)

C) stan!ar! .y!rogen electro!e 3S/ )

.he most %undamental re%erence electrode in electrochemistry) MNy de%initionM its e$uilibrium potential is considered (ero at any temperature# because this electrode &as chosen as an arbitrary (ero point %or electrode potentials) ! (ero point is needed since the potential o% a single electrode cannot be measured# only the di%%erence o% t&o electrode potentials is measurable) !ll electrode potentials are e<pressed on this Mhydrogen scale)M It is a hydrogen electrode &ith an electrolyte containing unit concentration o% hydrogen ions and saturated &ith hydrogen gas at unit atmosphere pressure) .his electrode can be some&hat incon enient to use because o% the need to supply hydrogen gas) .here%ore# other re%erence electrodes (e)g)# calomel or sil erAsil er chloride) are o%ten used instead# but the measured electrode potentials can be con erted to the Mhydrogen scale)M !lso called Mnormal hydrogen electrode)M Strictly spea8ing# one must use unit acti ity rather than concentration o% hydrogen ions and unit %ugacity rather than unit pressure o% hydrogen gas) Pt E HD(g# =)0 atm)EHG(a$# A= =)0') O HD(g# =)0 atm) = HG(a$# A= =)0') G e Eo = 0)000 K

)oltage ,onversions 4et5een Di22erent 'e2erence Scales

I% an electrode has a potential o% 0)>:=K &ith respect to a calomel electrode# &hat is the potential &ith respect to a sil er-sil er chloride electrodeP Qhat &ould be the potential &ith respect to the standard hydrogen electrodeP

Li6ui!-7unction 1otential
! potential di%%erence bet&een t&o solutions o% di%%erent compositions separated by a membrane type separator) .he simplest e<ample is the case o% t&o solutions containing the same salt in di%%erent concentrations) .he salt &ill di%%use %rom the higher concentration side to the lo&er concentration side) Ho&e er# the di%%usion rate o% the cation and the anion o% the salt &ill ery seldom be e<actly the same (see mobility)) 0et us assume %or this e<ample that the cations mo e %asterR conse$uently# an e<cess positi e charge &ill accumulate on the lo& concentration side# &hile an e<cess negati e charge &ill accumulate on the high concentration side o% the Bunction due to the slo& mo ing anions) .his sets up a potential di%%erence that &ill start an electromigration o% the ions that &ill increase the net %lu< o% the anions and decrease the net %lu< o% the cations) In steady-sate conditions# the t&o ions &ill mo e at the same speed and a potential di%%erence &ill be created bet&een the t&o solutions) .his Msteady-sateM potential di%%erence seems constant# but this is misleading because it slo&ly changes as the concentrations bet&een the t&o solutions e$uali(e) .he di%%usion process &ill Me entuallyM result in e$ual concentrations o% the salt in the t&o solutions separated by the membrane# and the li$uid-Bunction potential &ill anish) 4or a simple case# the alue o% the li$uid Bunction potential can be calculated by the so called MHendersonM e$uation)

8unction 1otential @
a small potential that e<ists at the inter%ace bet&een t&o electrolyte solutions that di%%er in composition)

De elopment o% the Bunction potential caused by une$ual mobilities o% ions)

'obilties o% ions in &ater at D;oC@ +aG @ ;)=9 L =0 FJ mDAsK IG @ S):D L =0 FJ ClF @ S)9=L =0 FJ

Fig 21-- Diagram o% a sil erAsil er chloride electrode

sho&ing the parts o% the electrode that produce the re%erence electrode potential , re% and the Buction potential ,B

Fig" 21-9" Sc.ematic re1resentation o2 a li6ui! 7unction s.o5ing t.e source o2 t.e 7unction 1otential: 7" $.e lengt. o2 t.e arro5s corres1on!s to t.e relative mobilities o2 t.e ions"

Li6ui! 7unction 1otential

Cells &ithout li$uid Bunction PtAHD&g'# HClA!gClA!g -are to ha e this type o% cell Cells &ith li$uid Bunction 2lass %rit Salt bridge De elop a potential by di%%erential migration rates o% the cation and anion) Tunction potential HCl(0)=)AHCl(0)0=) ICl(0)=)AICl(0)0=) ,B = >0 mK (HG %aster than ClF ) ,B = F=)0 mK (IG slo&er than ClF )

*sually e<perimentally determine instrument response

In!icator electro!es
(etallic indicator electrode re! ond! to anal"te activit") lectro!e o2 t.e 2irst ty1e
Direct e$uilibrium &ith analyte !g %or !gG# !u %or !uCG# etc Potential described by +ernst e$uation) !s 7'? # , VnG(a*) G ne = V(!) ,ind = ,o F (0);9=:An) log (=A7VnG?)

+ote potential linearly related to log o% the concentration U -emember - indicator N3 D,4I+I.I/+ cathode measurement theoretically under (ero-current (steady state) ! plot o% ,$uation D=-C %or an electrode o% the %irst 8ind)

lectro!e o2 t.e secon! ty1e

Indirect e$uilibrium &ith analyte 'A'VAVF Sil erASil er chloride %or chloride also +ernstian response as 7VF? # ,

!gCl(s) G e = !g(s) G ClF(a*) ,ind = ,o F 0);9=: log 7ClF?

Inert &etallic electro!e 2or 'e!o; systems

Pro ides a sur%ace %or the electrochemistry to occur Pt# !u# Pd# C

! plot o% ,$uation D=-> %or an electrode o% the second 8ind %or ClF)

In!icator electro!es
Indicator electrodes %or potentiometric measurements are o% t&o basic types# namely# $etallic and $e$+rane)

1) &etallic in!icator electro!es < de elop a potential that is determined by the e$uilibrium position o% redo< hal%-reaction at the electrode sur%ace) First-or!er electro!es 2or cations @ ! %irst order electrode is comprised o% a metal immersed in a solution o% its ions# such as sil er &ire dipping into a sil er nitrate solution) /nly a %e& metals such as !ilver, co er, $erc,r", lead , -inc, +i!$,th, cad$i,$ and tin e<hibit re ersible hal%- reactions &ith their ions and are suitable %or use as %irst order electrodes) /ther metals# including iron, nickel, co+alt, t,ng!ten, and chro$i,$# de elop nonreproducible potentials that are in%luenced by impurities and crystal irregularities in the solid and by o<ide coatings on their sur%aces) .his nonreproducible beha ior ma8es them unsatis%actory as %irstorder electrodes)

;am1le o2 2irst or!er metallic in!icator electro!es

.he outer compartment o% the electrode is %illed &ith I+/C# so there is no direct contact bet&een Cl- in the inner compartment and !gG in the bea8er

$.e reaction at t.e *g in!icator electro!e is !gG G e- !g(s) ,oG = 0)S99 K $.e calomel re2erence .al2-cell reaction is HgDClD(s) G De- DHg(l) G D Cl - ,W = 0)D>= K .he re%erence potential is %i<ed at 0)D>=K because the re%erence cell is saturated &ith ICl) .he +ernst e$uation %or the entire cell is there%ore
, = ,G - , = X0)S99-0)0;9=: log ( =*g>?)Y - X0)D>=Y Potential o% !g E !gG Indicator electrode Potential o% S)C), re%erence electrode
1

@ 0"99A 0"09B1C log 31/=*g>?)

I!eally: t.e voltage c.anges by 9B"1Cm) 3at 29 ) 2or eac. 2actor-o2-10 c.ange in =*g>?
*se o% !g and calomel electrode to measure 7!gG?

Secon!-or!er electro!es 2or anions ! metal electrode can sometimes be indirectly responsi e to the concentration o% an anion that %orms a reci itate or co$ le% ion &ith cations o% the metal) ,<) =) Sil er electrode .he potential o% a sil er electrode &ill accurately re%lect the concentration o% iodide ion in a solution that is saturated &ith sil er iodide) !gI(s) G e = !g(s) G IF Eo = F 0)=;=K

E = F 0)=;= F (0)0;9=:A=) log 7IF? = F 0)=;= G (0)0;9=:A=)pI D) 'ercury electrode %or measuring the concentration o% the ,D.! anion 3 >F) 'ercury electrode responds in the presence o% a small concentration o% the stable ,D.! comple< o% mercury(II)) Hg3DF G De = Hg(l) G 3>F Eo = 0)D=K E = 0)D= F (0)0;9=:AD) log (73>F? A7Hg3DF?)

Inert electro!es Chemically inert conductors such as gold, latin,$# or car+on that do not participate# directly# in the redo< process are called inert electrodes) .he potential de eloped at an inert electrode depends on the nature and concent-ration o% the arious redo< reagents in the solution)
!g(s) E !gCl7satHd?# ICl7%'? E E 4eDG#4eCG) E Pt 4eCGGe = 4eDG Eo = G0)SS0K Ecell = Eindicator F Ere%erence = X0)SS0 F (0)0;9=:A=) log 74eDG?A74eCG?Y F X0)DDD F (0)0;9=:A=) log 7ClF?Y

2) &embrane in!icator electro!es

.he potential de eloped at this type o% electrode results %rom an une$ual charge buildup at opposing sur%ace o% a special membrane) .he charge at each sur%ace is go erned by the position o% an e$uilibrium in ol ing analyte ions# &hich# in turn# depends on the concentration o% those ions in the solution)

.he electrodes are categori(ed according to the type o% membrane they employ @ glass# polymer# crystalline# gas sensor)
.he %irst practical glass electrode) (Haber and Ilemensie&c(# .) /h"!) Che$# =909# :;# CJ;)

&embrane in!icator electro!es

0lass membrane 1/ electro!es

.he internal element consists o% sil er-sil er chloride electrode immersed in a pH S bu%%er saturated &ith sil er chloride) .he thin# ion-selecti e glass membrane is %used to the bottom o% a sturdy# nonresponsi e glass tube so that the entire membrane can be submerged during measurements) Qhen placed in a solution containing hydrogen ions# this electrode can be represented by the hal%cell @

!g(s) E !gCl7satHd?# ClF(inside)# HG(inside) E glass membrane E HG(outside)

E = Eo F (0)0;9=:A=) log 7ClF? G (0)0;9=:A=) log (7HG(outside)?A7HG (inside)?) E = Q G (0)0;9=:A=) log 7HG(outside)?

1/ &eter
pH meter is a olt meter that measures the electrical potential di%%erence bet&een a pH electrode and a re%erence electrode and displays the result in terms o% pH alue o% the sample solution in &hich they are immersed Intro!uction .he pH meter measures the pH o% a solution using an ion-selecti e electrode (IS,) that responds to the HG concentration o% the solution) .he pH electrode produces a oltage that is proportional to the concentration o% the H G concentration# and ma8ing measurements &ith a pH meter is there%ore a %orm o% potentiometry) .he pH electrode is attached to control electronics &hich con ert the oltage to a pH reading and displays it on a meter) Instrumentation ! pH meter consists o% a HG-selecti e membrane# an internal re%erence electrode# an e<ternal re%erence electrode# and a meter &ith control electronics and display) Commercial pH electrodes usually combine all electrodes into one unit that are then attached to the pH meter)

.ypical electrode system %or measuring pH) (a) 2lass electrode (indicator) and saturated calomel electrode (re%erence) immersed in a solution o% un8no&n pH) (b) Combination probe consisting o% both an indicator glass electrode and a sil erAsil er chloride re%erence) ! second sil erAsil er chloride electrode ser es as the internal re%erence %or the glass electrode) .he t&o electrodes are arranged concentrically &ith the internal re%erence in the center and the e<ternal re%erence outside) .he re%erence ma8es contact &ith the analyte solution through the glass %rit or other suitable porous medium) Combination probes are the most common con%iguration o% glass electrode and re%erence %or measuring pH)

pH Meters

1/ meter # A gla!! co$+ination electrode

E 0 1 2 + (3)34567) log ( Ain 8 Ao,t )

1 @ A!"$$etr" otential + @ electro$otive efficienc" ( close to =)00) A @ Activit" of h"drogen ion

Composition o% glass membranes S0Z Si/D C0Z Ca/# Na/# 0iD/# +aD/# andAor !lD/C Ion e<change process at glass membrane-solution inter%ace@ 2lF G HG = HG2lF

(a) Cross-sectional ie& o% a silicate glass structure) In addition to the three Si/ bonds sho&n# each silicon is bonded to an additional o<ygen atom# either abo e or belo& the plane o% the paper) (b) 'odel sho&ing threedimensional structure o% amorphous silica &ith +aG ion (large dar8 blue) and se eral HG ions small dar8 blue incorporated)

Potential o2 t.e glass electro!e

.he potential di%%erence across the glass pH electrode depends on the acti ity o% HG on each side o% the glass membrane)

,m = K= F KD = (-.A4)lna= F (-.A4)lnaD = ,asym G 0)0;9=: log(a= A aD) i% A= = constant# ,m = I G 0)0;9=: loga= = I F 0)0;9=: pH
Standardi(ation at pH=S)00 # , = 0 K) pH >)00# ,= ;9)=: mKApH unit
Potential pro%ile across a glass membrane %rom the analyte solution to the internal re%erence solution) .he re%erence electrode potentials are not sho&n)

=00oC S> mKApH unit ;00 ,(mK) 0 Isopotential point 0oC ;> mKApH unit

S pH

=>

,alibrating a glass electro!e

=) !l&ays 8eep the electrodes in distilled &ater# saturated ICl solution(C)S') or bu%%er &hen not in use) D) Po&er /+) S&itch to [S.!+DN3\ @ allo& to &arm %or C0 min) C) -inse the electrode thoroughly &ith distilled &ater and then &ith pH S)00 bu%%er solution) Nlot &ith clean tissue) >) Determine the temperature o% the bu%%er solution &ith a thermometer) !dBust [.,'P,-!.*-,\ 8nob on the unit to the temperature) ;) Place the electrode in pH S)00 (isopotential point) bu%%er solution) -otate the selector s&itch to [pH\) Qait %or a stable display) Ny using [C!0IN-!.I/+\ 8nob# set the meter to the pH alue o% the bu%%er at its measured temperature) S&itch to [S.!+DN3\ :) -inse the electrode thoroughly &ith distilled &ater and then &ith pH >)00 bu%%er solution) Nlot &ith clean tissue) S) Place the electrode in pH >)00 bu%%er solution) -otate the selector s&itch to [pH\) Qait %or a stable display) *sing [S0/P,\ 8nob# set the meter to the pH alue o% the bu%%er at its measured temperature) S&itch to [S.!+DN3\

,alibration o2 t.e &eters 5it. 1/ D an! 1/ 2 4u22ers =) Select the pH 'ode and set the temperature control 8nob to D;]C) !dBust the cal D 8nob to read =00Z) D) -inse the electrode &ith deioni(ed &ater and blot dry using a piece o% tissue (Shur&ipes or Iim&ipes are a ailable in the labs)) C) Place the electrode in the solution o% pH S bu%%er# allo& the display to stabili(e and# then# set the display to read S by adBusting cal =) -emo e the electrode %rom the bu%%er) >) -inse the electrode &ith deioni(ed &ater and blot dry using a piece o% tissue (Shur&ipes or Iim&ipes are a ailable in the labs)) ;) Place the electrode in the solution o% pH D bu%%er# allo& the display to stabili(e and# then# set the display to read D by adBusting cal D) -emo e the electrode %rom the bu%%er) :) -inse the electrode &ith deioni(ed &ater and blot dry using a piece o% tissue (Shur&ipes or Iim&ipes# as be%ore)) %#$ - Nu%%er solution are made a ailable to you in indi idually labeled D o() bottles) .he bu%%ers are to be used in these containers# onlyU Do not pour them into other containers at any time) !%ter use# cap the bottles so that the bu%%ers can be re-used)

&easuring 1/
=) 'a8e sure that the meter is set to the pH 'ode and adBust the temperature to D;]C) D) Place the electrode in the sample to be tested) C) .he pH o% the solution appears in the display) +/.,@ !llo& the display to stabili(e be%ore ta8ing your readingU >) -inse the pH electrode and place it bac8 in the storage solution)

rrors t.at a22ect 1/ measurements 5it. glass electro!e

=) .he al8aline(sodium) error @ lo& readings at pH alues greater than 9 D) .he acid error @ some&hat high &hen the pH is less than about 0); C) Dehydration may cause erratic electrode per%ormance) >) Kariation in Bunction potential @ ^ 0)0= pH unit ;) ,rror in the pH o% the standard bu%%er @ 0)0= pH unit

,leaning glass electro!e @

=) Qashing &ith :' HCl D) D0 &A&Z a$ueous ammonium bi%luoride (+H >H4D)

!cid and al8aline errors %or selected glass electrodes at D; )

(4rom -)2) Nates# Deter$ination of 9, Dnd ed)# p) C:;)) +e& 3or8@ Qiley# =9SC))

Ion-Selective lectro!es 3IS )

Intro!uction !n Ion-Selecti e ,lectrode (IS,) produces a potential that is proportional to the concentration o% an analyte) 'a8ing measurements &ith an IS, is there%ore a %orm o% potentiometry) .he most common IS, is the pH electrode# &hich contains a thin glass membrane that responds to the HG concentration in a solution) $.eory .he potential di%%erence across an ion-sensiti e membrane is@ , = I F (D)C0C-.An4)log(a) &here I is a constant to account %or all other potentials# - is the gas constant# . is temperature# n is the number o% electrons trans%erred# 4 is 4araday5s constant# and a is the acti ity o% the analyte ion) ! plot o% measured potential ersus log( a) &ill there%ore gi e a straight line) IS,s are susceptible to se eral inter%erences) Samples and standards are there%ore diluted =@= &ith total ionic strength adBuster and bu%%er (.IS!N)) .he .IS!N consists o% = ' +aCl to adBust the ionic strength# acetic acidAacetate bu%%er to control pH# and a metal comple<ing agent)

IS 3ion selective electro!e)

!ny electrode that pre%erentially responds to one ion species)

=) 2lass membrane electrode @ HG D) 0i$uid membrane electrodes C) Solid state and precipitate electrodes >) 2as sensing electrodes ;) ,n(yme electrodes

Selecti ity coe%%icient kV#3 = (response to 3) A (response to V)

2eneral beha ior o% IS, , = constant (0)0;9=:AnV) log 7AV G(kV#3 A3 nV n3 )?

Instrumentation IS,s consist o% the ion-selecti e membrane# an internal re%erence electrode# an e<ternal re%erence electrode# and a oltmeter) ! typical meter is sho&n in the document on the pH meter) Commercial IS,s o%ten combine the t&o electrodes into one unit that are then attached to a pH meter)

Schematic o% an IS, measurement

Picture o% a commercial %luoride IS,

http@AA&&&)chemistry)adelaide)edu)auAe<ternalASoc--elAContentAise)htm

Li6ui! IS Ca IS,
Calcium didecylphosphate dissol ed in dioctylphenylphosphonate

7(CHC(CHC)JCHD/)DP/D?DCa

D7(CHC(CHC)JCHD/)DP/D?F G CaDG

Diagram o% a li$uid-membrane electrode %or CaDG)

Comparison o% a li$uid-membrane calcium ion electrode &ith a glass pH electrode)

Photograph o% a potassium li$uid-ion e<changer microelectrode &ith =D; m o% ion e<changer inside the tip) .he magni%ication o% the original photo &as >00L)

! homemade li$uid-membrane electrode)

Soli! state crystalline membrane electro!e

'igration o% 4F through 0a4C doped &ith ,u4D)

;am1le< Fluori!e 3F-) electro!e

Internal re% electrode !gA!gCl 4illing soln) !$ueous +aCl G +a4 'embrane 0a4C crystal disc !pplications ,lectroplating industry# &ater treatment (%luoridation)# toothpaste

*11lications o2 ion selective electro!es Ion-selecti e electrodes are used in a &ide ariety o% applications %or determining the concentrations o% arious ions in a$ueous solutions) .he %ollo&ing is a list o% some o% the main areas in &hich IS,s ha e been used) Pollution 'onitoring@ C+# 4# S# Cl# +/C etc)# in e%%luents# and natural &aters) !griculture@ +/C# Cl# +H># I# Ca# I# C+ in soils# plant material# %ertilisers and %eedstu%%s) 4ood Processing@ +/C# +/D in meat preser ati es) Salt content o% meat# %ish# dairy products# %ruit Buices# bre&ing solutions) 4 in drin8ing &ater and other drin8s) Ca in dairy products and beer) I in %ruit Buices and &ine ma8ing) Corrosi e e%%ect o% +/C in canned %oods) Detergent 'anu%acture@ Ca# Na# 4 %or studying e%%ects on &ater $uality) Paper 'anu%acture@ S and Cl in pulping and reco ery-cycle li$uors) ,<plosi es@ 4# Cl# +/C in e<plosi e materials and combustion products) ,lectroplating@ 4 and Cl in etching bathsR S in anodising baths) Niomedical 0aboratories@ Ca# I# Cl in body %luids (blood# plasma# serum# s&eat)) 4 in s8eletal and dental studies)

Semi-con!uctor
Imper%ections or impurities in &hat are normally insulators may gi e rise to a temperature-dependent conducti ity( metallic conducti ity decreases &ith rise in temperature) arising because the highest occupied energy le el is ery close to an unoccupied le el)

Classi%ication semiconductor conductor insulator

speci%ic resistance =0F> ^ =0S _m ^=0FJ =0=D^=0D0

,lemental or intrinsic semiconductor @ ten nine (99)99999999Z purity)

II

III N !l

IK C Si 2e Sn

KI

P !s Sb

1n Cd

2a In

Se .e

Compounds or e<trinsic impurity semiconductor IK`III or K III`K II`KI SiC SiP Si!s SiSb# SiN# Si!l

!lP# !l!s# !lSb# 2aP# 2a!s# 2aSb# InP# In!s# InSb 1nS# 1nSe# 1n.e# CdS# CdSe# Cd.e

p-ty1e an! n-ty1e semicon!uctor

hole

carrier Conduction electron

Si Si Si

Si Si Si

Si Si Si

Si Si Si

Si !l Si

Si Si Si

Si Si Si

Si P Si

Si Si Si

Complete co alent bond

Displaced by tri alent(acceptor) impurity atom

Displaced by penta alent(donor) impurity atom

Pure silicon crystal structure

-type

n-type

Dio!e <

electron tube# e acuated glass or metal en elope containing t&o electrodes# a cathode and an anode) It is used as a recti%ier and as a detector in electronic circuits such as radio and tele ision recei ers) Qhen a positi e oltage is applied to the anode (or plate)# electrons emitted %rom the heated cathode %lo& to the plate and return to the cathode through an e<ternala

Depletion region

Dio!e < p-n 7unction

hole

Conduction electron

n
4or&ard bias current %lo&

n
-e erse bias +o current %lo&

n G G

F F
Cathode mar8

Dr) Tohn Nardeen# Dr) Qalter Nrattain# and Dr) Qilliam Shoc8ley disco ered the transistor e%%ect and de eloped the %irst de ice in December# =9>S# &hile the three &ere members o% the technical sta%% at Nell 0aboratories in 'urray Hill# +T) .hey &ere a&arded the +obel Pri(e in physics in =9;:)
http@AA&&&)lucent)comAmindsAtransistorA Copyright 2002 Lucent Technologies. All rights reserved. *

$ransistor
!n acti e component o% an electronic circuit &hich may be used as an ampli%ier# detector# or s&itch) ! transistor consists o% a small bloc8 o% semiconducting material to &hich at least three electrical contacts are made) .ransistors are o% t&o general types# bipolar and %ield e%%ect)

:n: type
emitter base collector

n: :n type
emitter base collector

Carrier@ hole C N , N C ,

Carrier@ conduction electron

.ransistor ,miter Collector Nase Nase Carrier ( ) !" #$ %&'( )* +, -. ) /01 +, -.2 *nipolar .ransistor Nipolar .ransistor 2 34'5 # 67 # 89 # :" ; <=> ?@A B ) '/S('etal /<ide Semiconductor) +, = CDEA F$G H = I ( J ) A KL MN2 # +-'/S P-'/S O PQ ) '/S 4,.(4ield ,%%ect .ransistor) ( ) RS .- T UVEA CDEN2 F$W UV (XF 4,. YZ01 M [) 4,.( RS X\'<] @ ^_`a .ransistor @ 4ield ,%%ect .ransistor) ( ^bcd ) eG Carrier fA . ; g ( hi ) j G3 klG .ransistor) . g Carrier fA G Nipolar YGe *nipola( mn ) .ransisor o pq[ ) 4,. RS X\'<Xr sN2 4ield ,%%ecti e .ransistor t.5 uvw X\'<X x') y? zp {+ X\'<X |< }lG (X (2ate) ~Y o 1 (Drain) S -< (Source) ~ ( D[ ) H 8 '/S4,. YA f P 2 Y o 1<X (,nhancement) FS p (Depletion) F ' P[ ) ; '/S4,. # ~ #$I ; 9S G 4,. 9 #$A ' P[ <= - S o X\ P[ ) '/S4,. 9 % #$ ~ I$ % '<X Y~ A I2N.(Insulated 2ate Ni-polar .ransistor) 8 @

0ate =) p2 .ransistor Ge )* F 2 G5 # D 9 g K } F$ p 2 ) D) +, > '/S .ransistor KA G = .2 Nipolar .ransistor Nase }lG . ) mitter +P+# P+P O F .ransistor 2 K +, ) ,ollector .ransistor 3 ) 4ase &aterial3 ) Z 2 F$ P $ ) -3 (carbon nanotube) p 2 (silicon microchip) A Y ,f MN2 1[ ) D00= J D: { o1 3] (+ano 0etter) } V IN' V- .) T) V] (.) T) Qatson -esearch Center) - > p< (Ph) ! ouris) (K) Deryc8e)# (-) 'artel)# &U (T) !ppen(eller) 2 $ V {E -3 (Single &all carbon nanotube R SQC+.s) @} RS X\'<] (%ield e%%ect transister R 4,.) $ (acti e cannel) A 2 ?G $[ )

Fiel! e22ect transistor

Drain 2ate Source

'/S4,.

channel

n channel

! metal o<ide %ield e%%ect transistor (&#SF $)) (a) Cross-sectional diagramR (b) circuit symbol)

!n ion-selcti e %ield e%%ect transistor (ISF $) %or measuring pH)

/peration o% a 2iel! e22ect transister) (a) +early random distribution o% holes and electrons in the base in the absence o% gate potential) (b) Positi e gate potential attracts electrons that %orm a conducti e channel beneath the gate) Current can %lo& through this channel bet&een source and drain)

/peration o% chemical-sensing %ield e%%ect transistor) .he transistor is coated &ith an insulating Si/D layer and a second layer o% Si+> (silicon nitride)# &hich is imper ious to ions and impro es electrical stability .he circuit at the lo&er le%t adBusts the potential di%%erence bet&een the re%erence electrode and the source in response to changes in the analyte solution# such that a constant drain-source current is maintained)

C/D gas sensing electrode

-esponse o% a li$uid-membrane electrode to ariations in the concentration and acti ity o% calcium ion)

!pparatus %or a potentiometric titration)

.itration o% D)>CCmmol o% chloride ion &ith 0)=000' sil er nitrate) (a) .itration cur e) (b) 4irst-deri ati e cur e) (c) Second-deri ati e cur e)

14
300

12

200

10

100

pH

mK
-100 -200 -300

2 0 5 10 15 20 25

-400 0 5 10 15 20 25

Kolume o% 0)= + +a/H (m0)

Kolume o% 0)= + +a/H (m0)

Experimental titration curve of 0.1 N HOAc with 0.1 N NaOH ( f = 0.9720 . C!.-0abASQ*# Dong-Sun 0ee

Thanks
Dong-Sun 0ee A C!. A SQ*